JP5333820B2 - Secondary battery negative electrode and secondary battery equipped with the same - Google Patents

Secondary battery negative electrode and secondary battery equipped with the same Download PDF

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JP5333820B2
JP5333820B2 JP2008135804A JP2008135804A JP5333820B2 JP 5333820 B2 JP5333820 B2 JP 5333820B2 JP 2008135804 A JP2008135804 A JP 2008135804A JP 2008135804 A JP2008135804 A JP 2008135804A JP 5333820 B2 JP5333820 B2 JP 5333820B2
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negative electrode
active material
secondary battery
electrode active
silicon
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JP2009283366A (en
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勇 小西池
浩太郎 佐鳥
賢一 川瀬
俊佑 倉澤
浩一 松元
貴一 廣瀬
正之 岩間
卓士 藤永
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ソニー株式会社
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    • HELECTRICITY
    • H01BASIC ELECTRIC ELEMENTS
    • H01MPROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00Electrodes
    • H01M4/02Electrodes composed of or comprising active material
    • H01M4/13Electrodes for accumulators with non-aqueous electrolyte, e.g. for lithium-accumulators; Processes of manufacture thereof
    • H01M4/134Electrodes based on metals, Si or alloys
    • HELECTRICITY
    • H01BASIC ELECTRIC ELEMENTS
    • H01MPROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M10/00Secondary cells; Manufacture thereof
    • H01M10/05Accumulators with non-aqueous electrolyte
    • H01M10/052Li-accumulators
    • HELECTRICITY
    • H01BASIC ELECTRIC ELEMENTS
    • H01MPROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M10/00Secondary cells; Manufacture thereof
    • H01M10/05Accumulators with non-aqueous electrolyte
    • H01M10/056Accumulators with non-aqueous electrolyte characterised by the materials used as electrolytes, e.g. mixed inorganic/organic electrolytes
    • H01M10/0564Accumulators with non-aqueous electrolyte characterised by the materials used as electrolytes, e.g. mixed inorganic/organic electrolytes the electrolyte being constituted of organic materials only
    • H01M10/0566Liquid materials
    • H01M10/0568Liquid materials characterised by the solutes
    • HELECTRICITY
    • H01BASIC ELECTRIC ELEMENTS
    • H01MPROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M10/00Secondary cells; Manufacture thereof
    • H01M10/05Accumulators with non-aqueous electrolyte
    • H01M10/056Accumulators with non-aqueous electrolyte characterised by the materials used as electrolytes, e.g. mixed inorganic/organic electrolytes
    • H01M10/0564Accumulators with non-aqueous electrolyte characterised by the materials used as electrolytes, e.g. mixed inorganic/organic electrolytes the electrolyte being constituted of organic materials only
    • H01M10/0566Liquid materials
    • H01M10/0569Liquid materials characterised by the solvents
    • HELECTRICITY
    • H01BASIC ELECTRIC ELEMENTS
    • H01MPROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00Electrodes
    • H01M4/02Electrodes composed of or comprising active material
    • H01M4/13Electrodes for accumulators with non-aqueous electrolyte, e.g. for lithium-accumulators; Processes of manufacture thereof
    • H01M4/139Processes of manufacture
    • H01M4/1395Processes of manufacture of electrodes based on metals, Si or alloys
    • HELECTRICITY
    • H01BASIC ELECTRIC ELEMENTS
    • H01MPROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00Electrodes
    • H01M4/02Electrodes composed of or comprising active material
    • H01M4/36Selection of substances as active materials, active masses, active liquids
    • H01M4/38Selection of substances as active materials, active masses, active liquids of elements or alloys
    • H01M4/386Silicon or alloys based on silicon
    • HELECTRICITY
    • H01BASIC ELECTRIC ELEMENTS
    • H01MPROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00Electrodes
    • H01M4/02Electrodes composed of or comprising active material
    • H01M4/36Selection of substances as active materials, active masses, active liquids
    • H01M4/58Selection of substances as active materials, active masses, active liquids of inorganic compounds other than oxides or hydroxides, e.g. sulfides, selenides, tellurides, halogenides or LiCoFy; of polyanionic structures, e.g. phosphates, silicates or borates
    • H01M4/5825Oxygenated metallic slats or polyanionic structures, e.g. borates, phosphates, silicates, olivines
    • HELECTRICITY
    • H01BASIC ELECTRIC ELEMENTS
    • H01MPROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00Electrodes
    • H01M4/02Electrodes composed of or comprising active material
    • H01M4/36Selection of substances as active materials, active masses, active liquids
    • H01M4/58Selection of substances as active materials, active masses, active liquids of inorganic compounds other than oxides or hydroxides, e.g. sulfides, selenides, tellurides, halogenides or LiCoFy; of polyanionic structures, e.g. phosphates, silicates or borates
    • H01M4/583Carbonaceous material, e.g. graphite-intercalation compounds or CFx
    • H01M4/587Carbonaceous material, e.g. graphite-intercalation compounds or CFx for inserting or intercalating light metals

Abstract

A secondary battery having high cycle characteristics is provided. The secondary battery includes a cathode, an anode, and an electrolyte. In the anode, an anode active material layer containing silicon, carbon, and oxygen as an anode active material is provided on an anode current collector. In the anode active material, a content of carbon is from 0.2 atomic % to 10 atomic % both inclusive, and a content of oxygen is from 0.5 atomic % to 40 atomic % both inclusive. A ratio from 0.1% to 17.29% both inclusive of the silicon contained in the anode active material exists as Si—C bond.

Description

The present invention relates to a negative electrode for a secondary battery containing a negative electrode active material containing silicon (Si) as a constituent element, and a secondary battery including the same.

  In recent years, many portable electronic devices such as a camera-integrated VTR (Videotape Recorder), a digital still camera, a mobile phone, a portable information terminal, or a notebook personal computer have appeared, and the size and weight of the portable electronic device have been reduced. Accordingly, development of secondary batteries that are lightweight and can obtain a high energy density as a power source for these electronic devices is underway. Among them, lithium ion secondary batteries using a carbon material for the negative electrode, a composite material of lithium (Li) and a transition metal for the positive electrode, and a carbonate ester for the electrolyte are compared with conventional lead batteries and nickel cadmium batteries. Since a large energy density can be obtained, it is widely used.

  Recently, with the improvement in performance of portable electronic devices, further improvement in capacity has been demanded, and the use of tin, silicon, or the like as a negative electrode active material instead of a carbon material has been studied (for example, , See Patent Document 1). This is because the theoretical capacity of tin is 994 mAh / g and the theoretical capacity of silicon is 4199 mAh / g, which is much larger than the theoretical capacity of graphite, 372 mAh / g, and an improvement in capacity can be expected.

  However, since the tin alloy or silicon alloy that occludes lithium has high activity, there is a problem that the electrolytic solution is easily decomposed and lithium is easily inactivated. Therefore, when charging / discharging is repeated, the charging / discharging efficiency decreases, and sufficient cycle characteristics cannot be obtained.

Therefore, it has been studied to form an inactive layer on the surface of the negative electrode active material. For example, it has been proposed to form a silicon oxide film on the surface of the negative electrode active material (Patent Document 2 and Patent Document). 3).
U.S. Pat. No. 4,950,566 JP 2004-171874 A JP 2004-319469 A

  Moreover, the negative electrode active material containing tin, silicon, or the like is accompanied by greater expansion and contraction than the case of being made of a carbon material such as graphite due to repeated charge and discharge. For this reason, the cycle characteristics may be deteriorated due to the collapse of the negative electrode active material itself or peeling from the negative electrode current collector.

In order to solve such a problem, cycle characteristics are improved by employing an electrode using an amorphous material containing at least one impurity selected from carbon, oxygen, nitrogen, argon, and fluorine together with silicon as an active material. Such a technique has been proposed (see, for example, Patent Document 4). As similar to this, Patent Document 5 discloses an active material having a composition represented by the general formula SiCxOy (x = 0.05 to 0.90, y = 0 to 0.9). Yes.
JP-A-2005-235397 JP 2007-184252 A

  However, when a silicon oxide film is provided as in Patent Documents 2 and 3, if the thickness is increased, the reaction resistance increases and the cycle characteristics become insufficient. Therefore, it is difficult to obtain sufficient cycle characteristics by the method of forming a film made of silicon oxide on the surface of a highly active negative electrode active material, and further improvement has been desired.

  In addition, as in Patent Documents 4 and 5, even when carbon or oxygen is contained in an active material mainly composed of silicon, in some cases, sufficient cycle characteristics cannot actually be obtained.

The present invention has been made in view of the above problems, its object is to provide a secondary battery using the negative electrode and the negative electrode for the secondary battery for a secondary battery capable of improving the cycle characteristics .

The negative electrode for secondary battery of the present invention, the anode current collector, one negative electrode active material, or a compound of silicon containing carbon and oxygen compounds of silicon containing compounds and oxygen of silicon are mixed containing-carbon or A negative electrode active material layer including a negative electrode active material having at least a part of two or more phases is provided. In the negative electrode active material, the carbon content is 0.4 atomic% or more and 3.9 atomic%. Ri is content der less than 11.0 atom% 25.0 atom% of oxygen with which less, there 3.64% 0.37% or more silicon contained in the anode active material below a Si-C bond It is what you do.

The secondary battery of the present invention includes an electrolyte together with a positive electrode and a negative electrode, and the negative electrode for a secondary battery of the present invention is used as the negative electrode.

According to the negative electrode for a secondary battery of the present invention, a predetermined amount of carbon and oxygen is added to the negative electrode active material layer containing silicon provided in the negative electrode current collector, and 0. 0 % of silicon contained in the negative electrode active material . Since 37% or more and 3.64% or less exist as Si—C bonds, the adhesion of the negative electrode active material layer to the negative electrode current collector can be improved. Moreover, the negative electrode active material layer becomes physically strong. For this reason, when this negative electrode for secondary batteries is used for electrochemical devices, such as the secondary battery of this invention, the outstanding cycling characteristics can be acquired.

  Hereinafter, embodiments of the present invention will be described in detail with reference to the drawings.

  FIG. 1 shows a cross-sectional configuration of a negative electrode according to an embodiment of the present invention. This negative electrode is used for, for example, an electrochemical device such as a battery, and includes a negative electrode current collector 101 having a pair of opposed surfaces, and a negative electrode active material layer 102 provided on the negative electrode current collector 101. doing.

  The negative electrode current collector 101 is preferably made of a material having good electrochemical stability, electrical conductivity, and mechanical strength. Examples of this material include metal materials such as copper (Cu), nickel (Ni), and stainless steel. Among these, copper is preferable. This is because high electrical conductivity can be obtained.

  The negative electrode active material layer 102 contains a negative electrode material containing all of silicon (Si), carbon (C), and oxygen (O) capable of inserting and extracting an electrode reactant as a negative electrode active material. Accordingly, a conductive agent or a binder may be included. Silicon has a large ability to occlude and release lithium, and a high energy density can be obtained. The negative electrode active material layer 102 may be provided on both surfaces of the negative electrode current collector 101 or may be provided on one surface.

The negative electrode material containing all of silicon, carbon, and oxygen includes a silicon compound containing carbon (eg, SiC) and a silicon compound containing oxygen (eg, Si 2 N 2 O, SiO v (0 <v ≦ 2) or LiSiO). Or a material having at least a part of one or two or more phases of a silicon compound containing carbon and oxygen. Here, in addition to silicon, carbon and oxygen, tin (Sn), nickel (Ni), copper (Cu), iron (Fe), cobalt (Co), manganese (Mn), zinc (Zn), indium (In) , Silver (Ag), titanium (Ti), germanium (Ge), bismuth (Bi), antimony (Sb), boron (B), magnesium (Mg), molybdenum (Mo), calcium (Ca), nitrogen (N) , Niobium (Nb), tantalum (Ta), vanadium (V), tungsten (W), lithium (Li), and chromium (Cr) may be included.

  In the negative electrode active material, the carbon content is 0.2 atomic% to 10 atomic% and the oxygen content is 0.5 atomic% to 40 atomic%. In particular, it is desirable that the carbon content is 0.4 atomic% to 5 atomic% and the oxygen content is 3 atomic% to 25 atomic%. Moreover, 0.1% or more and 17.29% or less of silicon contained in the negative electrode active material exists as Si—C bonds.

  An example of a measurement method for examining the bonding state of carbon in the negative electrode active material is X-ray photoelectron spectroscopy (XPS). The Si—C bond and the Si—Si bond are identified by X-ray photoelectron spectroscopy. From the ratio of the peak intensity due to the Si—C bond and the peak intensity due to the Si—Si bond, among the silicon contained in the negative electrode active material, The proportion existing as Si—C bonds can be determined. Specifically, for example, Si of silicon contained in the negative electrode active material is determined based on the intensity ratio between the Si—C bond component of the 1s orbital (C1s) peak of carbon bonded to silicon and the 2p orbital (Si2p) peak of silicon. The proportion present as -C bonds can be determined. In addition, since the silicon carbide compound exists only in a compound (SiC) having a composition ratio of Si: C = 1: 1, the amount of silicon (Si) having a Si—C bond is the amount of carbon having a Si—C bond ( It can be said that it is equal to the amount of C).

  The negative electrode active material layer 102 may have a single layer structure or a multilayer structure. In the case of a multilayer structure, a plurality of first and second layers having different oxygen contents may be alternately stacked. This is because it is suitable for obtaining higher cycle characteristics when used in an electrochemical device such as a secondary battery. Further, since the negative electrode active material layer 102 is formed in several degrees during manufacturing, it is easy to adjust the oxygen content, which is difficult to control by a single film formation, such as adjusting the degree of oxidation between the layers. Become. In addition, when the oxygen content in the negative electrode active material layer 102 is large, the stress of the negative electrode active material formed on the negative electrode current collector 101 tends to be large, but it should be formed in several degrees. Since the stress of the negative electrode active material is relaxed, it is possible to manufacture a negative electrode with good handleability in a desired composition.

  The negative electrode active material layer 102 may further include one or more other negative electrode materials capable of inserting and extracting an electrode reactant as a negative electrode active material. Examples of the other negative electrode material include a material that can occlude and release an electrode reactant and includes at least one of a metal element and a metalloid element as a constituent element. The other negative electrode material may be a single element, an alloy or a compound of a metal element or a metalloid element, or may have at least a part of one or more phases thereof. In addition, in addition to what consists of 2 or more types of metal elements, the alloy here also contains what contains 1 or more types of metal elements and 1 or more types of metalloid elements. Moreover, the alloy here may contain the nonmetallic element. This structure includes a solid solution, a eutectic (eutectic mixture), an intermetallic compound, or a mixture of two or more of them.

  Examples of other metal elements or metalloid elements constituting the negative electrode material include metal elements or metalloid elements capable of forming an alloy with the electrode reactant. Specifically, magnesium (Mg), boron (B), aluminum (Al), gallium (Ga), indium (In), germanium (Ge), tin (Sn), lead (Pb), bismuth (Bi), Examples thereof include cadmium (Cd), silver (Ag), zinc (Zn), hafnium (Hf), zirconium (Zr), yttrium (Y), palladium (Pd), and platinum (Pt).

Further, as the other negative electrode material, a simple substance of silicon or an alloy of silicon may be included. As an alloy of silicon, for example, as a second constituent element other than silicon, among the group consisting of tin, nickel, copper, iron, cobalt, manganese, zinc, indium, silver, titanium, germanium, bismuth, antimony and chromium You may make it contain at least 1 sort (s) of these. Further, as the other negative electrode material, a silicon compound containing no carbon and oxygen may be included. Examples of silicon alloys or compounds include SiB 4 , SiB 6 , Mg 2 Si, Ni 2 Si, TiSi 2 , MoSi 2 , CoSi 2 , NiSi 2 , CaSi 2 , CrSi 2 , Cu 5 Si, FeSi 2 , MnSi. 2, NbSi 2, TaSi 2, VSi 2, such as WSi 2, ZnSi 2 or Si 3 N 4.

  The negative electrode active material layer 102 containing silicon, carbon, and oxygen as a negative electrode material is formed using a vacuum deposition method, and the negative electrode active material layer 102 and the negative electrode current collector 101 are alloyed at least at a part of the interface. Is preferred. Specifically, the constituent elements of the negative electrode current collector 101 diffuse into the negative electrode active material layer 102 at the interface, the constituent elements of the negative electrode active material layer 102 diffuse into the negative electrode current collector 101, or the constituent elements thereof It is preferred that they diffuse together. This is because breakage due to expansion and contraction of the negative electrode active material layer 102 due to charge / discharge is suppressed, and electronic conductivity between the negative electrode active material layer 102 and the negative electrode current collector 101 is improved. Examples of the vacuum deposition method include an electron beam deposition method (electron beam heating deposition method) and a resistance heating method.

  Then, the manufacturing method of this negative electrode is demonstrated. For this negative electrode, a negative electrode current collector 101 is prepared, and if necessary, the surface thereof is roughened, and then the negative electrode current collector 101 is subjected to the electron beam evaporation apparatus (hereinafter simply referred to as vapor deposition) shown in FIG. It is manufactured by forming a negative electrode active material layer 102 containing silicon, carbon and oxygen by a vacuum deposition method using a device.

  FIG. 2 is a schematic diagram illustrating a configuration of a vapor deposition apparatus suitable for manufacturing the negative electrode of the present embodiment. This vapor deposition apparatus evaporates the vapor deposition materials 32A and 32B accommodated in the crucibles 31A and 31B, and the negative electrode current collector 101 as a deposition target made of a strip-shaped metal foil or the like held on the can rolls 4A and 4B. The negative electrode active material layer 102 is formed by depositing on the surface.

  The vapor deposition apparatus includes an evaporation source 3A and 3B, can rolls (film forming rolls) 4A and 4B, shutters 6A and 6B, take-up rollers 7 and 8, guide rollers 9 to 13 and feed rollers. A roller 14 is provided. A vacuum exhaust device 15 is provided outside the vapor deposition treatment tank 2.

  The vapor deposition treatment tank 2 is partitioned by a partition plate 16 into evaporation source installation chambers 2A and 2B and a deposition object traveling chamber 2C. The evaporation source installation chamber 2A and the evaporation source installation chamber 2B are separated by a partition wall 17. In addition to the evaporation source 3A, a shutter 6A is installed in the evaporation source installation chamber 2A, and in addition to the evaporation source 3B, a shutter 6B is installed in the evaporation source installation chamber 2B. Details of these evaporation sources 3A and 3B and shutters 6A and 6B will be described later. Moreover, the vapor deposition treatment tank 2 is provided with a gas inlet (not shown) so that oxygen gas can be supplied.

  Can rolls 4A and 4B are installed above the evaporation sources 3A and 3B, respectively, in the deposition object traveling chamber 2C. However, the partition plate 16 is provided with openings 161 and 162 at two locations corresponding to the can rolls 4A and 4B, and a part of the can rolls 4A and 4B protrudes into the evaporation source installation chambers 2A and 2B. Yes. Further, in the deposition object traveling chamber 2C, winding rollers 7 and 8, guide rollers 9 to 13, and a feed roller 14 are provided as means for holding the negative electrode current collector 101 and traveling in the longitudinal direction thereof, respectively. It is arranged at a predetermined position.

  Here, the negative electrode current collector 101 is in a state in which one end side thereof is wound up by, for example, the take-up roller 7, and the guide roller 9, the can roll 4 </ b> A, the guide roller 10, and the feed roller 14 in order from the take-up roller 7. The other end side is attached to the take-up roller 8 via the guide roller 11, the guide roller 12, the can roll 4 </ b> B, and the guide roller 13. The negative electrode current collector 101 is disposed so as to be in contact with the outer peripheral surfaces of the winding rollers 7 and 8, the guide rollers 9 to 13, and the feed roller 14. In addition, one surface (front surface) of the negative electrode current collector 101 is in contact with the can roll 4A, and the other surface (back surface) is in contact with the can roll 4B. Since the take-up rollers 7 and 8 are a drive system, the negative electrode current collector 101 can be sequentially conveyed from the take-up roller 7 to the take-up roller 8 and at the same time, be sequentially conveyed from the take-up roller 8 to the take-up roller 7. It is possible. 2 corresponds to a state in which the negative electrode current collector 101 travels from the take-up roller 7 to the take-up roller 8, and an arrow in the figure indicates a direction in which the negative electrode current collector 101 moves. Yes. Furthermore, in this vapor deposition apparatus, the feed roller 14 is also a drive system.

  The can rolls 4A, 4B are, for example, cylindrical rotating bodies (drums) for holding the deposition object 1, and by rotating (spinning), a part of the outer circumferential surface thereof is sequentially evaporated into the evaporation source installation chambers 2A, It enters 2B and faces the evaporation sources 3A and 3B. Here, in the outer peripheral surfaces of the can rolls 4A and 4B, the portions 41A and 41B that have entered the evaporation source installation chambers 2A and 2B are vapor deposition regions in which thin films are formed by the vapor deposition materials 32A and 32B from the evaporation sources 3A and 3B Become.

  The evaporation sources 3A and 3B are obtained by accommodating vapor deposition materials 32A and 32B containing single-crystal silicon and carbon in crucibles 31A and 31B made of, for example, boron nitride (BN), and the vapor deposition materials 32A and 32B are heated. Evaporates (vaporizes). Specifically, the evaporation sources 3A and 3B further include, for example, an electron gun (not shown), and the thermoelectrons emitted by driving the electron gun are electromagnetically generated by, for example, a deflection yoke (not shown). The vapor deposition materials 32A and 32B accommodated in the crucibles 31A and 31B are irradiated while being controlled in the range. The vapor deposition materials 32A and 32B are heated by irradiation with thermoelectrons from the electron gun, and after being melted, gradually evaporate.

  The crucibles 31A and 31B are made of, for example, an oxide such as titanium oxide, tantalum oxide, zirconium oxide, or silicon oxide in addition to boron nitride, and the crucibles 31A and 31B are irradiated with thermionic electrons irradiated to the vapor deposition materials 32A and 32B. In order to protect against an excessive temperature rise, a part of the periphery (for example, the bottom surface) may be configured to contact a cooling system (not shown). As the cooling system, for example, a water-cooled cooling device such as a water jacket is suitable.

  The shutters 6A and 6B are disposed between the evaporation sources 3A and 3B and the can rolls 4A and 4B, and are vapor-phase-deposited from the crucibles 31A and 31B toward the negative electrode current collector 101 held by the can rolls 4A and 4B. This is a mechanism that can be opened and closed to control the passage of the substances 32A and 32B. In other words, it is in an open state during the vapor deposition process, and allows passage of vapor-phase vapor deposition materials 32A and 32B evaporated from the crucibles 31A and 31B, while blocking the passage before and after the vapor deposition process. The shutters 6A and 6B are connected to a control circuit system (not shown), and are driven when a command signal for opening or closing is input.

  In order to manufacture the negative electrode of the present embodiment using this vapor deposition apparatus, it is performed as follows. Specifically, first, the wound product of the negative electrode current collector 101 is attached to the take-up roller 7, the end on the outer peripheral side is pulled out, and the end is guided to the guide roller 9, the can roll 4 </ b> A, the guide roller 10, The feed roller 14, the guide roller 11, the guide roller 12, the can roll 4 </ b> B, and the guide roller 13 are sequentially passed through and attached to a fitting portion (not shown) of the take-up roller 8.

Next, evacuation is performed by the vacuum evacuation device 15 so that the degree of vacuum inside the vapor deposition treatment tank 2 becomes a predetermined value (for example, about 10 −3 Pa). At this time, the shutters 6A and 6B are closed. With the shutters 6A and 6B closed, the vapor deposition materials 32A and 32B accommodated in the crucibles 31A and 31B are heated to start evaporation (vaporization). In this state, observation of the evaporation rate of the vapor deposition materials 32A and 32B accommodated in the crucibles 31A and 31B is started by a crystal monitor or the like (not shown), and the evaporation rate is reached when a predetermined time has elapsed since the evaporation was started. It is determined whether or not has reached the target value and whether or not it has stabilized. Therefore, when it has been confirmed that the evaporation rate has reached the target value and is stable, the winding roller 8 and the like are driven while introducing a predetermined amount of oxygen gas into the vapor deposition treatment tank 2. The traveling of the negative electrode current collector 101 is started and the shutters 6A and 6B are opened. As a result, the vapor deposition materials 32A and 32B pass through the opened shutters 6A and 6B to reach the negative electrode current collector 101 held by the can rolls 4A and 4B, and to both surfaces of the negative electrode current collector 101. The vapor deposition is started. As a result, the negative electrode active material layer 102 having a predetermined thickness can be formed by adjusting the traveling speed of the negative electrode current collector 101 and the evaporation rate of the vapor deposition materials 32A and 32B.

  Here, the case where the negative electrode active material layer 102 is formed on the negative electrode current collector 101 while performing traveling from the winding roller 7 to the winding roller 8 (referred to as forward traveling for convenience) has been described. The negative electrode active material layer 102 may be formed while traveling in the opposite direction, that is, while traveling the negative electrode current collector 101 from the winding roller 8 toward the winding roller 7. In that case, the take-up rollers 7 and 8, the guide rollers 9 to 13, the feed roller 14, and the can rolls 4A and 4B may be rotated in the reverse direction. In addition, the negative electrode active material layer 102 may be formed at a time by one run of the negative electrode current collector 101. However, in order to form the negative electrode active material layer 102 having a multilayer structure, a plurality of times may be used. It is necessary to perform vapor deposition over traveling. At that time, by adjusting the amount of oxygen gas introduced into the vapor deposition treatment tank 2, a negative electrode active material layer 102 having a multilayer structure in which a plurality of first and second layers having different oxygen contents are alternately laminated is formed. can do.

  According to the negative electrode of this embodiment, a predetermined amount of carbon and oxygen is added to the negative electrode active material layer 102 containing silicon provided in the negative electrode current collector 101, and 0.1% of silicon contained in the negative electrode active material is added. % Or more and 17.29% or less exist as Si—C bonds, so that the adhesion of the negative electrode active material layer 102 to the negative electrode current collector 101 can be improved. Further, the negative electrode active material layer 102 itself is physically strong. For this reason, when this negative electrode is used in an electrochemical device such as a secondary battery, the electrical resistance between the negative electrode current collector 101 and the negative electrode active material layer 102 decreases, and lithium is efficiently occluded and charged during charging and discharging. In addition to being released, collapse of the negative electrode active material layer 102 due to charge / discharge is suppressed, so that excellent cycle characteristics can be obtained. In particular, since the negative electrode active material layer 102 contains silicon, it is advantageous for increasing the capacity.

  Next, usage examples of the above-described negative electrode will be described. Here, taking a secondary battery as an example of an electrochemical device, the negative electrode is used as follows.

(First secondary battery)
3 and 4 show a cross-sectional configuration of the first secondary battery. FIG. 4 shows an enlarged part of the spirally wound electrode body 20 shown in FIG. The secondary battery described here is, for example, a lithium ion secondary battery in which the capacity of the negative electrode 122 is expressed based on insertion and extraction of lithium.

  The secondary battery mainly includes a wound electrode body 120 in which a positive electrode 121 and a negative electrode 122 are wound via a separator 123 inside a substantially hollow cylindrical battery can 111, and a pair of insulating plates 112, 113 is housed. The battery structure including the battery can 111 is called a cylindrical type.

  The battery can 111 is made of, for example, a metal material such as iron, aluminum, or an alloy thereof. One end of the battery can 111 is closed and the other end is opened. The pair of insulating plates 112 and 113 are arranged so as to extend perpendicular to the winding peripheral surface with the winding electrode body 120 interposed therebetween.

  A battery lid 114 and a safety valve mechanism 115 and a heat sensitive resistance element (Positive Temperature Coefficient: PTC element) 116 provided inside the battery can 111 are caulked through a gasket 117 and attached to the open end of the battery can 111. ing. Thereby, the inside of the battery can 111 is sealed. The battery lid 114 is made of the same material as the battery can 111, for example. The safety valve mechanism 115 is electrically connected to the battery lid 114 via the heat sensitive resistance element 116. In this safety valve mechanism 115, when the internal pressure becomes a certain level or more due to an internal short circuit or external heating, the disk plate 115A is reversed and the electric power between the battery lid 114 and the wound electrode body 120 is reversed. Connection is broken. The heat-sensitive resistance element 116 limits the current by increasing the resistance according to the temperature rise, and prevents abnormal heat generation due to a large current. The gasket 117 is made of, for example, an insulating material, and asphalt is applied to the surface thereof.

  A center pin 124 may be inserted in the center of the wound electrode body 120. In the wound electrode body 120, a positive electrode lead 125 made of a metal material such as aluminum is connected to the positive electrode 121, and a negative electrode lead 126 made of a metal material such as nickel is connected to the negative electrode 122. . The positive electrode lead 125 is welded to the safety valve mechanism 115 and electrically connected to the battery lid 114, and the negative electrode lead 126 is welded to and electrically connected to the battery can 111.

In the positive electrode 121, for example, a positive electrode active material layer 121B is provided on both surfaces of a positive electrode current collector 121A having a pair of surfaces. The positive electrode current collector 121A is made of, for example, a metal material such as aluminum, nickel, or stainless steel. Note that the positive electrode active material layer 121B includes a positive electrode active material, and may include other materials such as a binder and a conductive agent as necessary.

The positive electrode active material includes one or more positive electrode materials capable of inserting and extracting lithium as an electrode reactant. As the positive electrode material, for example, a lithium-containing compound is preferable. This is because a high energy density can be obtained. Examples of the lithium-containing compound include a composite oxide containing lithium and a transition metal element, or a phosphate compound containing lithium and a transition metal element. In particular, cobalt, nickel, manganese, and iron are used as the transition metal element. Those containing at least one of the group consisting of: This is because a higher voltage can be obtained. The chemical formula is represented by, for example, Li x M1O 2 or Li y M2PO 4 . In the formula, M1 and M2 represent one or more transition metal elements. The values of x and y vary depending on the charge / discharge state of the secondary battery, and are generally 0.05 ≦ x ≦ 1.10 and 0.05 ≦ y ≦ 1.10.

Examples of the composite oxide containing lithium and a transition metal element include lithium cobalt composite oxide (Li x CoO 2 ), lithium nickel composite oxide (Li x NiO 2 ), and lithium nickel cobalt composite oxide (Li x Ni). (1-z) Co z O 2 (z <1)), lithium nickel cobalt manganese composite oxide (Li x Ni (1-vw) Co v Mn w O 2 (v + w <1)), or spinel type structure And a lithium manganese composite oxide (LiMn 2 O 4 ). Among these, a complex oxide containing cobalt is preferable. This is because high capacity can be obtained and excellent cycle characteristics can be obtained. Examples of the phosphate compound containing lithium and a transition metal element include a lithium iron phosphate compound (LiFePO 4 ) or a lithium iron manganese phosphate compound (LiFe (1-u) Mn u PO 4 (u <1). ) And the like.

  In addition, examples of the positive electrode material include oxides such as titanium oxide, vanadium oxide and manganese dioxide, disulfides such as titanium disulfide and molybdenum sulfide, chalcogenides such as niobium selenide, sulfur, polyaniline or Examples also include conductive polymers such as polythiophene.

  The negative electrode 122 has a configuration similar to that of the negative electrode described above. For example, the negative electrode active material layer 122B is provided on both surfaces of a negative electrode current collector 122A having a pair of surfaces. The configurations of the negative electrode current collector 122A and the negative electrode active material layer 122B are the same as the configurations of the negative electrode current collector 101 and the negative electrode active material layer 102 in the above-described negative electrode, respectively. In the negative electrode 122, it is preferable that the charge capacity of the negative electrode material capable of inserting and extracting lithium is larger than the charge capacity of the positive electrode 121. This is because even when fully charged, the possibility that lithium is deposited as dendrites on the negative electrode 122 is reduced.

  The separator 123 separates the positive electrode 121 and the negative electrode 122, and allows lithium ions to pass through while preventing a short circuit of current due to contact between the two electrodes. The separator 123 is made of, for example, a porous film made of a synthetic resin such as polytetrafluoroethylene, polypropylene, or polyethylene, or a porous film made of ceramic, and these two or more kinds of porous films are laminated. It may be what was done. Among these, a porous film made of polyolefin is preferable because it is excellent in short-circuit preventing effect and can improve the safety of the secondary battery due to the shutdown effect. In particular, polyethylene is preferable because a shutdown effect can be obtained at 100 ° C. or higher and 160 ° C. or lower and the electrochemical stability is excellent. Polypropylene is also preferable, and other resins having chemical stability may be copolymerized with polyethylene or polypropylene, or may be blended.

  The separator 123 is impregnated with an electrolytic solution that is a liquid electrolyte. This electrolytic solution contains a solvent and an electrolyte salt dissolved in the solvent.

  The solvent contains, for example, one or more of nonaqueous solvents such as organic solvents. Examples of the non-aqueous solvent include ethylene carbonate, propylene carbonate, butylene carbonate, dimethyl carbonate, diethyl carbonate, ethyl methyl carbonate, methyl propyl carbonate, γ-butyrolactone, γ-valerolactone, 1,2-dimethoxyethane, tetrahydrofuran, 2-methyltetrahydrofuran, tetrahydropyran, 1,3-dioxolane, 4-methyl-1,3-dioxolane, 1,3-dioxane, 1,4-dioxane, methyl acetate, ethyl acetate, methyl propionate, ethyl propionate, Methyl butyrate, methyl isobutyrate, methyl trimethylacetate, ethyl trimethylacetate, acetonitrile, glutaronitrile, adiponitrile, methoxyacetonitrile, 3-methoxypropionitrile, N, N-dimethylformamide, N-methylpyrrolidinone, N -Methyloxazolidinone, N, N'-dimethylimidazolidinone, nitromethane, nitroethane, sulfolane, trimethyl phosphate or dimethyl sulfoxide. Among these, at least one selected from the group consisting of ethylene carbonate, propylene carbonate, dimethyl carbonate, diethyl carbonate, and ethyl methyl carbonate is preferable. This is because excellent capacity characteristics, cycle characteristics and storage characteristics can be obtained. In this case, in particular, a high viscosity (high dielectric constant) solvent such as ethylene carbonate or propylene carbonate (for example, relative dielectric constant ε ≧ 30) and a low viscosity solvent such as dimethyl carbonate, ethyl methyl carbonate or diethyl carbonate (for example, A combination with (viscosity ≦ 1 mPa · s) is more preferable. This is because the dissociation property of the electrolyte salt and the ion mobility are improved, so that a higher effect can be obtained.

  This solvent preferably contains a cyclic carbonate having an unsaturated bond represented by Chemical Formulas 1 to 3. This is because high cycle characteristics can be obtained. These may be used alone or in combination.

(R11 and R12 are a hydrogen group or an alkyl group.)

(R13 to R16 are a hydrogen group, an alkyl group, a vinyl group or an allyl group, and at least one of them is a vinyl group or an allyl group.)

(R17 is an alkylene group.)

  The cyclic ester carbonate having an unsaturated bond shown in Chemical Formula 1 is a vinylene carbonate-based compound. Examples of the vinylene carbonate compound include vinylene carbonate (1,3-dioxol-2-one), methyl vinylene carbonate (4-methyl-1,3-dioxol-2-one), and ethyl vinylene carbonate (4-ethyl). -1,3-dioxol-2-one), 4,5-dimethyl-1,3-dioxol-2-one, 4,5-diethyl-1,3-dioxol-2-one, 4-fluoro-1, Examples thereof include 3-dioxol-2-one and 4-trifluoromethyl-1,3-dioxol-2-one. Among these, vinylene carbonate is preferable. This is because it is easily available and a high effect can be obtained.

  The cyclic ester carbonate having an unsaturated bond shown in Chemical Formula 2 is a vinyl ethylene carbonate compound. Examples of the vinyl carbonate-based compound include vinyl ethylene carbonate (4-vinyl-1,3-dioxolan-2-one), 4-methyl-4-vinyl-1,3-dioxolan-2-one, and 4-ethyl. -4-vinyl-1,3-dioxolan-2-one, 4-n-propyl-4-vinyl-1,3-dioxolan-2-one, 5-methyl-4-vinyl-1,3-dioxolane-2 -One, 4,4-divinyl-1,3-dioxolan-2-one, 4,5-divinyl-1,3-dioxolan-2-one, and the like. Among these, vinyl ethylene carbonate is preferable. This is because it is easily available and a high effect can be obtained. Of course, as R13 to R16, all may be vinyl groups, all may be allyl groups, or vinyl groups and allyl groups may be mixed.

  The cyclic ester carbonate having an unsaturated bond shown in Chemical Formula 3 is a methylene ethylene carbonate compound. Examples of the methylene ethylene carbonate compound include 4-methylene-1,3-dioxolan-2-one, 4,4-dimethyl-5-methylene-1,3-dioxolan-2-one, and 4,4-diethyl-5. -Methylene-1,3-dioxolan-2-one and the like. This methylene ethylene carbonate compound may have one methylene group (compound shown in Chemical Formula 3) or two methylene groups.

  The cyclic carbonate having an unsaturated bond may be catechol carbonate having a benzene ring in addition to those shown in Chemical Formulas 1 to 3. The content of the cyclic carbonate having an unsaturated bond in the solvent is preferably 0.01% by weight or more and 10% by weight or less. This is because a sufficient effect can be obtained.

  The solvent contains at least one of a chain carbonate having a halogen represented by Chemical Formula 4 as a constituent element and a cyclic carbonate having a halogen represented by Chemical Formula 5 as a constituent element. preferable. This is because a stable protective film is formed on the surface of the negative electrode 22 and the decomposition reaction of the electrolytic solution is suppressed, so that the cycle characteristics are improved.

(R21 to R26 are a hydrogen group, a halogen group, an alkyl group or a halogenated alkyl group, and at least one of them is a halogen group or a halogenated alkyl group.)

(R27 to R30 are a hydrogen group, a halogen group, an alkyl group or a halogenated alkyl group, and at least one of them is a halogen group or a halogenated alkyl group.)

  In addition, R21 to R26 in Chemical formula 4 may be the same or different. The same applies to R27 to R30 in Chemical Formula 5. Although the kind of halogen is not specifically limited, For example, at least 1 type in the group which consists of a fluorine, chlorine, and a bromine is mentioned, Among these, a fluorine is preferable. This is because a high effect can be obtained. Of course, other halogens may be used.

  The number of halogens is preferably two rather than one, and may be three or more. This is because the ability to form a protective film is increased and a stronger and more stable protective film is formed, so that the decomposition reaction of the electrolytic solution is further suppressed.

  Examples of the chain carbonate having a halogen shown in Chemical Formula 4 include fluoromethyl methyl carbonate, bis (fluoromethyl) carbonate, difluoromethyl methyl carbonate, and the like. These may be single and multiple types may be mixed.

  Examples of the cyclic carbonate having a halogen shown in Chemical formula 5 include a series of compounds represented by Chemical formula 6 and Chemical formula 7. That is, 4-fluoro-1,3-dioxolan-2-one of (1) shown in Chemical formula 6, 4-chloro-1,3-dioxolan-2-one of (2), 4,5 of (3) -Difluoro-1,3-dioxolan-2-one, (4) tetrafluoro-1,3-dioxolan-2-one, (5) 4-fluoro-5-chloro-1,3-dioxolane-2-one ON, (6) 4,5-dichloro-1,3-dioxolan-2-one, (7) tetrachloro-1,3-dioxolan-2-one, (8) 4,5-bistrifluoromethyl 1,3-dioxolan-2-one, 4-trifluoromethyl-1,3-dioxolan-2-one of (9), 4,5-difluoro-4,5-dimethyl-1,3 of (10) -Dioxolan-2-one, 4-methyl-5,5 of (11) Difluoro-1,3-dioxolan-2-one, and the like 5,5-difluoro-1,3-dioxolan-2-one (12). In addition, 4-trifluoromethyl-5-fluoro-1,3-dioxolan-2-one of (1) shown in Chemical Formula 7 and 4-trifluoromethyl-5-methyl-1,3-dioxolane of (2) 2-one, 4-fluoro-4,5-dimethyl-1,3-dioxolan-2-one of (3), 4,4-difluoro-5- (1,1-difluoroethyl)-of (4) 1,3-dioxolan-2-one, 4,5-dichloro-4,5-dimethyl-1,3-dioxolan-2-one in (5), 4-ethyl-5-fluoro-1, in (6) 3-dioxolan-2-one, 4-ethyl-4,5-difluoro-1,3-dioxolan-2-one of (7), 4-ethyl-4,5,5-trifluoro-1 of (8) , 3-Dioxolan-2-one, 4-fluoro-4-methyl-1 of (9) 3-dioxolan-2-one, and the like. These may be single and multiple types may be mixed.

  Of these, 4-fluoro-1,3-dioxolan-2-one or 4,5-difluoro-1,3-dioxolan-2-one is preferred, and 4,5-difluoro-1,3-dioxolan-2-one is preferred. More preferred. In particular, 4,5-difluoro-1,3-dioxolan-2-one is preferably a trans isomer rather than a cis isomer. This is because it is easily available and a high effect can be obtained.

  The electrolyte salt includes, for example, any one or more of light metal salts such as a lithium salt. Examples of the lithium salt include lithium hexafluorophosphate, lithium tetrafluoroborate, lithium perchlorate, and lithium hexafluoroarsenate. This is because excellent capacity characteristics, cycle characteristics and storage characteristics can be obtained. Among these, lithium hexafluorophosphate is preferable. This is because a higher effect can be obtained because the internal resistance is lowered.

  This electrolyte salt preferably contains at least one selected from the group consisting of compounds represented by Chemical Formulas 8 to 10. This is because a higher effect can be obtained when used together with the above-described lithium hexafluorophosphate or the like. In addition, R33 in Chemical formula 8 may be the same or different. The same applies to R41 to R43 in Chemical Formula 9 and R51 and R52 in Chemical Formula 10.

(X31 is a group 1 element or group 2 element in the long-period periodic table, or aluminum. M31 is a transition metal element, or a group 13 element, group 14 element, or group 15 element in the long-period periodic table. R31 Y31 is —OC—R32—CO—, —OC—C (R33) 2 — or —OC—CO—, wherein R32 is an alkylene group, a halogenated alkylene group, an arylene group or a halogen. R33 is an alkyl group, a halogenated alkyl group, an aryl group or a halogenated aryl group, wherein a3 is an integer of 1 to 4, b3 is 0, 2 or 4, and c3, d3, m3 and n3 are integers of 1 to 3)

(X41 is a group 1 element or group 2 element in the long-period periodic table. M41 is a transition metal element, or a group 13, element, or group 15 element in the long-period periodic table. Y41 is —OC. — (C (R41) 2 ) b4 —CO—, — (R43) 2 C— (C (R42) 2 ) c4 —CO—, — (R43) 2 C— (C (R42) 2 ) c4 —C ( R43) 2 —, — (R43) 2 C— (C (R42) 2 ) c4 —SO 2 —, —O 2 S— (C (R42) 2 ) d4 —SO 2 — or —OC— (C (R42 2 ) d4— SO 2 —, wherein R41 and R43 are a hydrogen group, an alkyl group, a halogen group or a halogenated alkyl group, and at least one of each is a halogen group or a halogenated alkyl group R42 is hydrogen group, alkyl group, halo. Or a4, e4 and n4 are 1 or 2, b4 and d4 are integers of 1 to 4, c4 is an integer of 0 to 4, and f4 and m4 are It is an integer from 1 to 3.)

(X51 is a group 1 element or group 2 element in the long-period periodic table. M51 is a transition metal element, or a group 13, element or group 15 element in the long-period periodic table. Rf is fluorinated. An alkyl group or a fluorinated aryl group, each having 1 to 10 carbon atoms Y51 is —OC— (C (R51) 2 ) d5 —CO—, — (R52) 2 C— (C (R51) 2) d5 -CO -, - ( R52) 2 C- (C (R51) 2) d5 -C (R52) 2 -, - (R52) 2 C- (C (R51) 2) d5 -SO 2 -, —O 2 S— (C (R51) 2 ) e5 —SO 2 — or —OC— (C (R51) 2 ) e5 —SO 2 —, wherein R51 is a hydrogen group, alkyl group, halogen group or halogen R52 represents a hydrogen group, an alkyl group, or a halo group. Or at least one of them is a halogen group or a halogenated alkyl group, wherein a5, f5 and n5 are 1 or 2, and b5, c5 and e5 are 1-4. D5 is an integer of 0 to 4, and g5 and m5 are integers of 1 to 3.)

  The group 1 elements in the long-period periodic table are hydrogen, lithium, sodium, potassium, rubidium, cesium, and francium. Group 2 elements are beryllium, magnesium, calcium, strontium, barium and radium. Group 13 elements are boron, aluminum, gallium, indium and thallium. Group 14 elements are carbon, silicon, germanium, tin and lead. Group 15 elements are nitrogen, phosphorus, arsenic, antimony and bismuth.

  Examples of the compound represented by Chemical formula 8 include the compounds represented by Chemical formulas (1) to (6). Examples of the compound represented by Chemical formula 9 include the compounds represented by Chemical formulas (1) to (8). Examples of the compound represented by Chemical formula 10 include the compound represented by Chemical formula 13 and the like. It is needless to say that the compound having the structure shown in Chemical Formula 8 to Chemical Formula 10 is not limited to the compound shown in Chemical Formula 11 to Chemical Formula 13.

  Moreover, it is preferable that electrolyte salt contains at least 1 sort (s) of the group which consists of a compound represented by Chemical formula 14-Chemical formula 16. This is because a higher effect can be obtained when used together with the above-described lithium hexafluorophosphate or the like. Note that m and n in Chemical formula 14 may be the same or different. The same applies to p, q and r in Chemical formula 16.

(M and n are integers of 1 or more.)

(R61 is a linear or branched perfluoroalkylene group having 2 to 4 carbon atoms.)

(P, q and r are integers of 1 or more.)

Examples of the chain compound shown in Chemical formula 14 include bis (trifluoromethanesulfonyl) imide lithium (LiN (CF 3 SO 2 ) 2 ), bis (pentafluoroethanesulfonyl) imide lithium (LiN (C 2 F 5 SO 2 ) 2 ), (trifluoromethanesulfonyl) (pentafluoroethanesulfonyl) imide lithium (LiN (CF 3 SO 2 ) (C 2 F 5 SO 2 )), (trifluoromethanesulfonyl) (heptafluoropropanesulfonyl) imide lithium ( LiN (CF 3 SO 2 ) (C 3 F 7 SO 2 )) or (trifluoromethanesulfonyl) (nonafluorobutanesulfonyl) imidolithium (LiN (CF 3 SO 2 ) (C 4 F 9 SO 2 )) Can be mentioned. These may be single and multiple types may be mixed.

  Examples of the cyclic compound represented by Chemical formula 15 include a series of compounds represented by Chemical formula 17. That is, 1,2-perfluoroethanedisulfonylimide lithium of (1) shown in Chemical formula 17, 1,3-perfluoropropane disulfonylimide lithium of (2), 1,3-perfluorobutane of (3) Disulfonylimide lithium, 1,4-perfluorobutane disulfonylimide lithium of (4), and the like. These may be single and multiple types may be mixed. Among these, 1,3-perfluoropropane disulfonylimide lithium is preferable. This is because a high effect can be obtained.

Examples of the chain compound shown in Chemical formula 16 include lithium tris (trifluoromethanesulfonyl) methide (LiC (CF 3 SO 2 ) 3 ).

  The content of the electrolyte salt is preferably 0.3 mol / kg or more and 3.0 mol / kg or less with respect to the solvent. This is because, outside this range, the ion conductivity may be extremely lowered.

  The electrolytic solution may contain various additives along with the solvent and the electrolyte salt. This is because the chemical stability of the electrolytic solution is further improved.

  Examples of the additive include sultone (cyclic sulfonic acid ester). This sultone is, for example, propane sultone or propene sultone, among which propene sultone is preferable. These may be single and multiple types may be mixed.

  Moreover, as an additive, an acid anhydride is mentioned, for example. Examples of the acid anhydride include carboxylic acid anhydrides such as succinic acid anhydride, glutaric acid anhydride and maleic acid anhydride, disulfonic acid anhydrides such as ethanedisulfonic acid anhydride and propanedisulfonic acid anhydride, Examples thereof include carboxylic acid and sulfonic acid anhydrides such as benzoic acid anhydride, sulfopropionic acid anhydride and sulfobutyric acid anhydride, among which sulfobenzoic acid anhydride and sulfopropionic acid anhydride are preferable. These may be single and multiple types may be mixed.

  This secondary battery is manufactured, for example, by the following procedure.

  First, the positive electrode 121 is manufactured. First, a positive electrode active material, a binder, and a conductive agent are mixed to form a positive electrode mixture, and then dispersed in an organic solvent to obtain a paste-like positive electrode mixture slurry. Subsequently, the positive electrode mixture slurry is uniformly applied to both surfaces of the positive electrode current collector 121A by a doctor blade or a bar coater and dried. Finally, the positive electrode active material layer 121B is formed by compression molding the coating film with a roll press or the like while heating as necessary. In this case, compression molding may be repeated a plurality of times.

  Further, the negative electrode 122 is manufactured by forming the negative electrode active material layer 122B on both surfaces of the negative electrode current collector 122A by the same procedure as the above-described negative electrode manufacturing procedure.

Next, the wound electrode body 120 is produced using the positive electrode 121 and the negative electrode 122. First, the positive electrode lead 125 is attached to the positive electrode current collector 121A by welding or the like, and the negative electrode lead 126 is attached to the negative electrode current collector 122A by welding or the like. After that, after the positive electrode 121 and the negative electrode 122 are laminated via the separator 123, the wound electrode body 120 is manufactured by winding in the longitudinal direction, and the center pin 124 is inserted into the center of the winding. Subsequently, the wound electrode body 120 is sandwiched between the pair of insulating plates 112 and 113 and accommodated in the battery can 111 , and the tip of the positive electrode lead 125 is welded to the safety valve mechanism 115, and the tip of the negative electrode lead 126 is attached. It welds to the battery can 111. Finally, after injecting the electrolyte into the battery can 111 and impregnating the separator 123, the battery lid 114, the safety valve mechanism 115, and the heat sensitive resistance element 116 are attached to the opening end of the battery can 111 via the gasket 117. Fix by caulking. Thereby, the secondary battery shown in FIGS. 3 and 4 is completed.

  In the secondary battery, when charged, for example, lithium ions are extracted from the positive electrode 121 and inserted in the negative electrode 122 through the electrolytic solution impregnated in the separator 123. On the other hand, when discharging is performed, for example, lithium ions are released from the negative electrode 122 and inserted into the positive electrode 121 through the electrolytic solution impregnated in the separator 123.

  According to this cylindrical secondary battery, the negative electrode 122 has the same configuration as the negative electrode of FIG. 1 described above, and is manufactured by the same method as the negative electrode manufacturing method described above. The adhesion of the negative electrode active material layer 122B to the negative electrode current collector 122A can be improved. Further, the negative electrode active material layer 122B itself is physically strong. For this reason, the electrical resistance between the negative electrode current collector 122A and the negative electrode active material layer 122B decreases, lithium is efficiently occluded and released during charge and discharge, and the negative electrode active material layer 122B collapses due to charge and discharge. It is suppressed. Furthermore, the reaction between the negative electrode active material and the electrolytic solution is suppressed by allowing 0.1% to 17.29% of silicon contained in the negative electrode active material to exist as Si—C bonds. For these reasons, excellent cycle characteristics can be obtained. Further, since the negative electrode 122 contains silicon, it is advantageous for increasing the capacity.

(Secondary secondary battery)
FIG. 5 shows an exploded perspective configuration of the second secondary battery, and FIG. 6 shows an enlarged cross section taken along line VI-VI of the spirally wound electrode body 130 shown in FIG. The secondary battery is, for example, a lithium ion secondary battery, similar to the first secondary battery described above, and the positive electrode lead 131 and the negative electrode lead 132 are mainly attached to the inside of the film-shaped exterior member 140. The wound electrode body 130 is accommodated. The battery structure including the exterior member 140 is called a laminate film type.

  For example, both the positive electrode lead 131 and the negative electrode lead 132 are led out in the same direction from the inside of the exterior member 140 toward the outside. The positive electrode lead 131 is made of, for example, a metal material such as aluminum, and the negative electrode lead 132 is made of, for example, a metal material such as copper, nickel, or stainless steel. These metal materials are, for example, in a thin plate shape or a mesh shape.

  The exterior member 140 is made of, for example, an aluminum laminate film in which a nylon film, an aluminum foil, and a polyethylene film are bonded together in this order. The exterior member 140 has, for example, a structure in which outer edges of two rectangular aluminum laminate films are bonded to each other by fusion or an adhesive so that a polyethylene film faces the wound electrode body 130. ing.

  An adhesion film 141 is inserted between the exterior member 140 and the positive electrode lead 131 and the negative electrode lead 132 in order to prevent intrusion of outside air. The adhesion film 141 is made of a material having adhesion to the positive electrode lead 131 and the negative electrode lead 132. Examples of this type of material include polyolefin resins such as polyethylene, polypropylene, modified polyethylene, and modified polypropylene.

  In addition, the exterior member 140 may be composed of a laminate film having another laminated structure instead of the above-described aluminum laminate film, or may be composed of a polymer film such as polypropylene or a metal film.

  The wound electrode body 130 is wound after the positive electrode 133 and the negative electrode 134 are stacked via the separator 135 and the electrolyte 136, and the outermost peripheral portion thereof is protected by the protective tape 137.

  FIG. 7 shows an enlarged part of the spirally wound electrode body 130 shown in FIG. In the positive electrode 133, for example, a positive electrode active material layer 133B is provided on both surfaces of a positive electrode current collector 133A having a pair of surfaces. The negative electrode 134 has the same configuration as the negative electrode described above. For example, the negative electrode active material layer 134B is provided on both surfaces of a negative electrode current collector 134A having a pair of surfaces. The configuration of the positive electrode current collector 133A, the positive electrode active material layer 133B, the negative electrode current collector 134A, the negative electrode active material layer 134B, and the separator 135 is the same as that of the positive electrode current collector 121A and the positive electrode active material layer in the first secondary battery described above. The configurations of 121B, the negative electrode current collector 122A, the negative electrode active material layer 122B, and the separator 123 are the same.

  The electrolyte 136 is a so-called gel electrolyte that contains an electrolytic solution and a polymer compound that holds the electrolytic solution. A gel electrolyte is preferable because high ion conductivity (for example, 1 mS / cm or more at room temperature) is obtained and liquid leakage is prevented.

  Examples of the polymer compound include ether-based polymer compounds such as polyethylene oxide, a crosslinked product containing polyethylene oxide, or polypropylene oxide, and acrylate-based or ester-based polymers such as polymethyl methacrylate, polyacrylic acid, or polymethacrylic acid. Compounds, polyvinylidene fluoride, copolymers of polyvinylidene fluoride and polyhexafluoropyrene, and fluorine-based polymer compounds such as polytetrafluoroethylene or polyhexafluoropropylene. In addition, polyacrylonitrile, polyphosphine Zen, polysiloxane, polyvinyl acetate, polyvinyl alcohol, styrene-butadiene rubber, nitrile-butadiene rubber, polystyrene, polycarbonate, etc.These may be single and multiple types may be mixed. Among these, as the polymer compound, a fluorine polymer compound such as polyvinylidene fluoride is preferable. This is because it has high redox stability and is electrochemically stable. The content of the polymer compound in the electrolyte varies depending on the compatibility with the electrolytic solution, but is preferably 5% by weight or more and 50% by weight or less, for example.

  The composition of the electrolytic solution is the same as the composition of the electrolytic solution in the first secondary battery. However, the solvent in this case is not only a liquid solvent but also a broad concept including those having ion conductivity capable of dissociating the electrolyte salt. Accordingly, when a polymer compound having ion conductivity is used, the polymer compound is also included in the solvent.

  Instead of the gel electrolyte 136 in which the electrolytic solution is held by the polymer compound, the electrolytic solution may be used as it is. In this case, the separator 135 is impregnated with the electrolytic solution.

  The secondary battery provided with the gel electrolyte 136 is manufactured by, for example, the following three methods.

  In the first manufacturing method, first, the positive electrode active material layer 133B is formed on both surfaces of the positive electrode current collector 133A, for example, by the same procedure as the positive electrode 121 and the negative electrode 122 in the first secondary battery described above. Thus, the positive electrode 133 is manufactured, and the negative electrode active material layer 134B is formed on both surfaces of the negative electrode current collector 134A to manufacture the negative electrode 134. Subsequently, a precursor solution containing an electrolytic solution, a polymer compound, and a solvent is prepared and applied to the positive electrode 133 and the negative electrode 134, and then the solvent is volatilized to form the gel electrolyte 136. Subsequently, the positive electrode lead 131 is attached to the positive electrode 133 and the negative electrode lead 132 is attached to the negative electrode 134. Subsequently, the positive electrode 133 and the negative electrode 134 on which the electrolyte 136 is formed are stacked via the separator 135 and then wound in the longitudinal direction, and the protective tape 137 is adhered to the outermost peripheral portion thereof to produce the wound electrode body 130. To do. Finally, for example, after sandwiching the wound electrode body 130 between two film-shaped exterior members 140, the outer edge portions of the exterior member 140 are bonded to each other by heat fusion or the like, so that the wound electrode body 130 is attached. Encapsulate. At this time, the adhesion film 141 is inserted between the positive electrode lead 131 and the negative electrode lead 132 and the exterior member 140. Thereby, the secondary battery shown in FIGS. 5 to 7 is completed.

  In the second manufacturing method, first, the positive electrode lead 131 is attached to the positive electrode 133 and the negative electrode lead 132 is attached to the negative electrode 134, and then the positive electrode 133 and the negative electrode 134 are stacked and wound via the separator 135. A protective tape 137 is adhered to the outer peripheral portion to produce a wound body that is a precursor of the wound electrode body 130. Subsequently, after sandwiching the wound body between the two film-like exterior members 140, the remaining outer peripheral edge portion except the outer peripheral edge portion on one side is adhered by thermal fusion or the like, so that the bag-like exterior The wound body is accommodated in the member 140. Subsequently, an electrolyte composition containing an electrolytic solution, a monomer that is a raw material of the polymer compound, a polymerization initiator, and other materials such as a polymerization inhibitor as necessary is prepared to form a bag-shaped exterior member. After injecting into the inside of 140, the opening of the exterior member 140 is sealed by thermal fusion or the like. Finally, the gel electrolyte 136 is formed by thermally polymerizing the monomer to obtain a polymer compound. Thereby, the secondary battery is completed.

  In the third manufacturing method, a wound body is formed by forming a wound body in the same manner as in the second manufacturing method described above, except that the separator 135 having the polymer compound coated on both sides is used first. It is housed inside 140. Examples of the polymer compound applied to the separator 135 include a polymer containing vinylidene fluoride as a component, that is, a homopolymer, a copolymer, or a multi-component copolymer. Specifically, polyvinylidene fluoride, binary copolymers containing vinylidene fluoride and hexafluoropropylene as components, and ternary copolymers containing vinylidene fluoride, hexafluoropropylene and chlorotrifluoroethylene as components. Such as coalescence. In addition, the high molecular compound may contain the other 1 type, or 2 or more types of high molecular compound with the polymer which uses the above-mentioned vinylidene fluoride as a component. Subsequently, after the electrolytic solution is prepared and injected into the exterior member 140, the opening of the exterior member 140 is sealed by thermal fusion or the like. Finally, the exterior member 140 is heated while applying a load, and the separator 135 is brought into close contact with the positive electrode 133 and the negative electrode 134 through the polymer compound. As a result, the electrolytic solution is impregnated into the polymer compound, and the polymer compound is gelled to form the electrolyte 136. Thus, the secondary battery is completed.

  In the third manufacturing method, the swollenness of the secondary battery is suppressed as compared with the first manufacturing method. Further, in the third manufacturing method, compared to the second manufacturing method, the monomer or solvent that is a raw material of the polymer compound is hardly left in the electrolyte 136, and the formation process of the polymer compound is well controlled. Therefore, sufficient adhesion is obtained between the positive electrode 133, the negative electrode 134, the separator 135, and the electrolyte 136.

  In this secondary battery, lithium ions are occluded and released between the positive electrode 133 and the negative electrode 134 as in the first battery. That is, when charged, for example, lithium ions are released from the positive electrode 133 and inserted into the negative electrode 134 through the electrolyte 136. On the other hand, when discharging is performed, for example, lithium ions are extracted from the negative electrode 134 and inserted into the positive electrode 133 through the electrolyte 136.

  According to this laminated film type secondary battery, the negative electrode 134 has the same configuration as the negative electrode shown in FIG. 1 described above, and is manufactured by the same method as the negative electrode manufacturing method described above. Therefore, cycle characteristics can be improved.

(Third battery)
8 and 9 show a cross-sectional configuration of the third secondary battery. The cross section shown in FIG. 8 and the cross section shown in FIG. 9 are in a positional relationship orthogonal to each other. That is, FIG. 9 is a cross-sectional view in the arrow direction along the line IX-IX shown in FIG. This secondary battery is a so-called prismatic battery, and is a lithium ion secondary battery in which a flat wound electrode body 160 is accommodated in an outer can 151 having a substantially hollow rectangular parallelepiped shape.

  The outer can 151 is made of, for example, iron (Fe) plated with nickel (Ni), and also has a function as a negative electrode terminal. The outer can 151 has one end closed and the other end opened, and the inside of the outer can 151 is sealed by attaching an insulating plate 152 and a battery lid 153 to the open end. The insulating plate 152 is made of polypropylene or the like, and is disposed on the wound electrode body 160 perpendicular to the winding peripheral surface. The battery lid 153 is made of, for example, the same material as that of the outer can 151 and has a function as a negative electrode terminal together with the outer can 151. A terminal plate 154 serving as a positive terminal is disposed outside the battery lid 153. Further, a through hole is provided near the center of the battery cover 153, and a positive electrode pin 155 electrically connected to the terminal plate 154 is inserted into the through hole. The terminal plate 154 and the battery lid 153 are electrically insulated by an insulating case 156, and the positive electrode pin 155 and the battery lid 153 are electrically insulated by a gasket 157. The insulating case 156 is made of, for example, polybutylene terephthalate. The gasket 157 is made of, for example, an insulating material, and the surface is coated with asphalt.

  In the vicinity of the periphery of the battery cover 153, a cleavage valve 158 and an electrolyte injection hole 159 are provided. The cleavage valve 158 is electrically connected to the battery lid 153, and is cleaved when the internal pressure of the battery exceeds a certain level due to an internal short circuit or external heating, thereby suppressing an increase in the internal pressure. . The electrolyte injection hole 159 is closed by a sealing member 159A made of, for example, a stainless steel ball.

  The wound electrode body 160 is formed by stacking a positive electrode 161 and a negative electrode 162 with a separator 163 therebetween and spirally wound, and is formed into a flat shape in accordance with the shape of the outer can 151. Yes. A separator 163 is positioned on the outermost periphery of the wound electrode body 160, and a positive electrode 161 is positioned immediately inside. In FIG. 10, a stacked structure of the positive electrode 161 and the negative electrode 162 is shown in a simplified manner. Further, the number of windings of the wound electrode body 160 is not limited to that shown in FIGS. 9 and 10 and can be arbitrarily set. A positive electrode lead 164 made of aluminum (Al) or the like is connected to the positive electrode 161 of the wound electrode body 160, and a negative electrode lead 165 made of nickel or the like is connected to the negative electrode 162. The positive electrode lead 164 is electrically connected to the terminal plate 154 by being welded to the lower end of the positive electrode pin 155, and the negative electrode lead 165 is welded and electrically connected to the outer can 151.

  As shown in FIG. 8, the positive electrode 161 has a positive electrode active material layer 161B provided on one or both surfaces of the positive electrode current collector 161A, and the negative electrode 162 has one surface of the negative electrode current collector 162A. Alternatively, the negative electrode active material layer 162B is provided on both surfaces. The configurations of the positive electrode current collector 161A, the positive electrode active material layer 161B, the negative electrode current collector 162A, the negative electrode active material layer 162B, and the separator 163 are respectively the positive electrode current collector 121A, the positive electrode active material layer 121B in the first battery described above. The configurations of the negative electrode current collector 122A, the negative electrode active material layer 122B, and the separator 123 are the same. The separator 163 is impregnated with the same electrolytic solution as the separator 123.

  This secondary battery can be manufactured as follows, for example.

Similar to the first battery described above, the wound electrode body 160 is formed by winding the positive electrode 161 and the negative electrode 162 through the separator 163, and then the wound body 160 is accommodated in the outer can 151. To do. Next, the insulating plate 152 is disposed on the wound electrode body 160, the negative electrode lead 165 is welded to the outer can 151, and the positive electrode lead 164 is welded to the lower end of the positive electrode pin 155 to open the open end of the outer can 151. The battery cover 153 is fixed to the substrate by laser welding. Finally, the electrolytic solution is injected into the outer can 151 from the electrolytic solution injection hole 159, impregnated in the separator 163, and the electrolytic solution injection hole 159 is closed with the sealing member 159A. Thereby, the secondary battery shown in FIGS. 8 and 9 is completed.

  According to this secondary battery, the negative electrode 162 has the same configuration as that of the negative electrode shown in FIG. 1 and is manufactured by the same method as the negative electrode manufacturing method described above. Characteristics can be improved.

  Examples of the present invention will be described in detail.

(Examples 1-21 to 1-31, 1-48 to 1-53, 1-61, Reference Examples 1-1 to 1-20, 1-32 to 1-47, 1-54 to 1-60, 1 -62 to 1-74)
The square secondary battery shown in FIGS. 8 and 9 was manufactured by the following procedure. At this time, a lithium ion secondary battery in which the capacity of the negative electrode 142 was expressed based on insertion and extraction of lithium was made.

First, the positive electrode 161 was produced. That is, lithium carbonate (Li 2 CO 3 ) and cobalt carbonate (CoCO 3 ) are mixed at a molar ratio of 0.5: 1 and then calcined in air at 900 ° C. for 5 hours. The product (LiCoO 2 ) was obtained. Subsequently, 96 parts by mass of a lithium / cobalt composite oxide as a positive electrode active material, 1 part by mass of graphite as a conductive agent, and 3 parts by mass of polyvinylidene fluoride as a binder were mixed to form a positive electrode mixture. -A paste-like positive electrode mixture slurry was prepared by dispersing in methyl-2-pyrrolidone. Finally, the positive electrode mixture slurry is uniformly applied to both surfaces of a positive electrode current collector 161A made of a strip-shaped aluminum foil (thickness = 15 μm), dried, and then compressed and molded by a roll press machine. A material layer 161B was formed. After that, a positive electrode lead 164 made of aluminum was welded to one end of the positive electrode current collector 161A.

  Next, the negative electrode 162 was produced. Specifically, after preparing a negative electrode current collector 162A (thickness = 20 μm, ten-point average roughness Rz = 3.5 μm) made of electrolytic copper foil, the vapor deposition apparatus of FIG. 1 described in the above embodiment is used. By depositing silicon as a negative electrode active material on both surfaces of the negative electrode current collector 162A by the electron beam evaporation method used, negative electrode active material particles were formed to have a single layer structure, and a negative electrode active material layer 162B was obtained. At this time, a deposition rate of 300 nm / second is used while continuously introducing oxygen gas into the vapor deposition treatment tank 2 using a single crystal silicon having a purity of 99.999% or more as an evaporation source and adding a predetermined amount of carbon. The negative electrode active material layer 162B having a thickness of 7 μm was formed. Here, the contents of carbon and oxygen contained as the negative electrode active material were made different for each example as shown in Tables 1 to 4 below. Specifically, the carbon content was in the range of 0.2 atomic% to 10 atomic%, and the oxygen content was in the range of 0.5 atomic% to 40 atomic%. Thereafter, a negative electrode lead 165 made of nickel was welded to one end of the negative electrode current collector 162A.

  Subsequently, a separator 163 made of a microporous polyethylene film having a thickness of 23 μm was prepared, and a positive electrode 161, a separator 163, a negative electrode 162, and a separator 163 were sequentially laminated to form a laminated body. The wound electrode body 160 was produced by winding a plurality of times in a spiral shape. The obtained wound electrode body 160 was formed into a flat shape.

Next, after the wound electrode body 160 molded into a flat shape is accommodated in the outer can 151, the insulating plate 152 is disposed on the wound electrode body 160 and the negative electrode lead 165 is welded to the outer can 151. At the same time, the positive electrode lead 144 was welded to the lower end of the positive electrode pin 155, and the battery lid 153 was fixed to the open end of the outer can 151 by laser welding. After that, the electrolytic solution was injected into the outer can 151 from the electrolytic solution injection hole 159. In the electrolyte, a solvent in which 30% by weight of ethylene carbonate (EC), 60% by weight of diethyl carbonate (DEC) and 10% by weight of vinylene carbonate (VC) were mixed, and LiPF 6 as an electrolyte salt at a concentration of 1 mol / dm 3 was used. What was dissolved in was used. Finally, the electrolyte injection hole 159 was closed with a sealing member 159A to obtain a square secondary battery.

(Comparative Examples 1-12)
Rechargeable batteries of Comparative Examples 1 to 12 were produced in the same manner as in Example 1 except that the contents of carbon and oxygen contained as the negative electrode active material were changed as shown in Table 1. . Specifically, the carbon content was outside the range of 0.2 atomic percent to 10 atomic percent, and the oxygen content was outside the range of 0.5 atomic percent to 40 atomic percent.

  The cycle characteristics of the secondary batteries of Examples and Comparative Examples produced in this manner were examined, and the bonding state of silicon contained in the negative electrode active material (the existence ratio as Si—C bonds) was also examined. These results are shown in Tables 1-5.

When examining the cycle characteristics, the discharge capacity retention rate was determined by performing a cycle test according to the following procedure. First, in order to stabilize the battery state, charge / discharge was performed for 1 cycle in an atmosphere at 25 ° C., and then charge / discharge was performed again to measure the discharge capacity at the second cycle. Subsequently, the discharge capacity at the 100th cycle was measured by charging and discharging 98 cycles in the same atmosphere. Finally, discharge capacity retention ratio (%) = (discharge capacity at the 100th cycle / discharge capacity at the second cycle) × 100 was calculated. At this time, for the first cycle, first, constant current charging was performed until the battery voltage reached 4.2 V at a constant current density of 0.2 mA / cm 2 , and then the current density was continuously maintained at a constant voltage of 4.2 V. until it reaches the 0.05 mA / cm 2 constant voltage charging, furthermore, the battery voltage at a constant current density of 0.2 mA / cm 2 was constant current discharge until it reaches the 2.5V. In addition, for one cycle after the second cycle, first, constant current charging is performed until the battery voltage reaches 4.2 V at a constant current density of 2 mA / cm 2 , and then the current density continues at a constant voltage of 4.2 V. The battery was charged at a constant voltage until reaching 0.1 mA / cm 2 , and further discharged at a constant current density of 2 mA / cm 2 until the battery voltage reached 2.5V.

  Regarding the investigation of the bonding state of carbon contained in the negative electrode active material, the Si—C bond and the Si—Si bond were identified by X-ray photoelectron spectroscopy using an Quantum 2000 photoelectron spectrometer manufactured by ULVAC-PHI. From the ratio between the peak intensity due to the C bond and the peak intensity due to the Si—Si bond, the ratio of the silicon contained in the negative electrode active material as Si—C bonds was determined. Specifically, it is as follows. First, in measuring the spectrum, an AlKα ray with an output of 25 W was used as an X-ray source. In addition, in order to obtain a bulk XPS spectrum of a negative electrode active material mainly composed of silicon, it is necessary to remove impurities such as an oxide film and a C—C bond covering the surface. Therefore, here, Ar ion beam etching was performed to remove the oxide film and impurities. The irradiation conditions of the Ar ion beam were an acceleration voltage of 1 kV and an incident angle of 45 °. Whether or not the oxide film was sufficiently removed was determined by measuring the XPS spectrum sequentially and observing the change. Whether or not the impurities were removed was judged based on the fact that peaks considered to be derived from C—H bonds and C—C bonds observed at around 284.5 eV were sufficiently reduced. Note that even if there are some impurities on the surface of the negative electrode active material, it is possible to separate peaks derived from Si—C bonds. When impurities are present on the surface of the negative electrode active material, in the spectrum of carbon 1s orbital (C1s), a peak (a) considered to be derived from a C—H bond and a C—C bond is observed around 284.5 eV, and C A peak (b) considered to be derived from the —Si bond was observed around 282.5 eV. In addition, a peak considered to be derived from a C—O bond or the like was observed in the vicinity of 286.5 eV. In order to separate these peaks, background subtraction using the Shirley function was performed, and peak fitting using a Gauss / Lorentz mixed function was further performed. At this time, the energy positions at the vertices of peak (a) and peak (b) were 284.5 eV ± 0.5 eV and 282.5 eV ± 0.5 eV, respectively. Using the fitting results, peak areas a and b of peak (a) and peak (b) were obtained, respectively. The energy correction on the horizontal axis of the XPS spectrum was such that the peak position of the carbon 1s orbit (C1s) was 284.5 eV. As a result, it is possible to separate the peak area b caused by the Si—C bond. Since silicon carbide includes only a compound (SiC) having a composition ratio of Si: C = 1: 1, the ratio of Si and C in the peak of the C—Si bond is assumed to be 1: 1. Further, the peak (c) of silicon 2p orbit (Si2p) observed in the vicinity of 99.1 eV was derived from the Si—Si bond, and the peak area c was determined. From the ratio of the peak area b to the peak area c, the proportion of silicon contained in the negative electrode active material that exists as Si—C bonds was determined.

  Further, each secondary battery after the charge / discharge cycle test was disassembled, and the amount of carbon and the amount of oxygen contained in each negative electrode active material layer 162B were measured as follows. At this time, the negative electrode active material layer 162B as a sample was cut away from a portion which is not opposed to the positive electrode, that is, lithium was not inserted or extracted. The copper foil as the negative electrode current collector 162A was not observed to contain carbon or oxygen. Therefore, the composition at this site is considered to be the same as the film composition immediately after film formation.

First, the amount of carbon was measured using a carbon / sulfur analyzer EMIA-520 manufactured by Horiba, Ltd. Specifically, a sample (1.0 g) taken out from a part of the negative electrode active material layer 162B is burned in an oxygen stream in a combustion furnace, and CO 2 , CO, and SO 2 generated at this time are converted into an oxygen stream. The carbon content (% by weight) was measured by detecting and integrating each gas concentration of CO 2 , CO, and SO 2 . In this non-dispersive infrared detector, an AC signal is transmitted corresponding to each gas concentration of CO 2 , CO, and SO 2 , this AC signal is converted into a digital value, and linearized and integrated by a microcomputer. . After integration, the blank value correction and sample weight correction are performed using a predetermined calibration formula, and the carbon / sulfur content (% by weight) is displayed.

On the other hand, the oxygen amount was measured using an oxygen / nitrogen analyzer EMGA-520,620 manufactured by Horiba, Ltd. Specifically, first, a sample (50 mg or more) taken out from a part of the negative electrode active material layer 162B is put into a high-temperature graphite crucible inside an extraction furnace held in a vacuum, and further heated. The sample is pyrolyzed. As a result, O in the sample, N, since each component of H are each CO, is discharged to the outside as N 2, H 2, their CO, non each gas N 2, H 2 by a carrier gas (He) Oxygen / nitrogen content (% by weight) was measured by conveying to a dispersed infrared detector and a thermal conductivity detector, and detecting CO with a non-dispersed infrared detector and N 2 with a thermal conductivity detector. In this non-dispersive infrared detector and thermal conductivity detector, an AC signal is transmitted corresponding to the detected concentration of gas (CO and N 2 ), this AC signal is converted into a digital value, and linearized by a microcomputer. And integration processing. After integration, the blank value correction and sample weight correction are performed using a predetermined calibration formula, and the oxygen / nitrogen content (% by weight) is displayed.

  Further, the content of silicon contained in the negative electrode active material layer 162B formed on the negative electrode current collector 162A was measured by an inductively coupled plasma emission spectrometer (ICP-AES). From the above measurement results, the carbon and oxygen content contained in the negative electrode active material layer 162B was calculated. The result is combined with Table 1-Table 5, and is shown.

  As shown in Tables 1 to 5, in this example, in the negative electrode active material, the carbon content was 0.2 atomic% or more and 10 atomic% or less, and the oxygen content was 0.5 atomic% or more. 40 atomic% or less, and 0.1% or more and 17.29% or less of silicon contained in the negative electrode active material exist as Si—C bonds, and therefore, excellent cycle characteristics can be exhibited as compared with the comparative example. It could be confirmed. In particular, in the negative electrode active material, more excellent cycle characteristics are exhibited by setting the carbon content to 0.4 atomic% to 5 atomic% and the oxygen content to 3 atomic% to 25 atomic%. I understood it. Also, overall, when the carbon content is high, the proportion of silicon existing as Si—C bonds decreases, and when the oxygen content is high, the proportion of silicon present as Si—C bonds tends to increase. Seem.

(Examples 2-1 and 2-5, Reference Examples 2-2 to 2-4 and 2-6)
The negative electrode active material layer 162B was the same as Example 1 except that the negative electrode active material layer 162B had a multi-layer structure of a total of 10 layers in which 5 layers of first and second layers having different oxygen contents were alternately laminated. A secondary battery was produced. However, the carbon and oxygen contents contained as the negative electrode active material were made different for each example as shown in Table 6 below.

  Regarding the secondary batteries of Examples 2-1 to 2-6, the cycle characteristics were examined, and the bonding state of carbon contained in the negative electrode active material (the existence ratio as Si—C bonds) was also examined. Furthermore, each secondary battery after the charge / discharge cycle test was disassembled, and the amount of carbon and the amount of oxygen contained in each negative electrode active material layer 162B were measured. These results are shown in Table 6.

  As shown in Table 6, it was found that by making the negative electrode active material layer 162B a multilayer structure, higher cycle characteristics can be obtained as compared with the case of a single layer structure. In the case of a multilayer structure, it seems that the proportion of silicon existing as Si—C bonds tends to increase compared to the case of a single layer structure.

(Examples 3-1 to 3-10)
A secondary battery was fabricated in the same manner as in Example 1 except that the composition of the electrolytic solution was changed. However, the contents of carbon and oxygen contained as the negative electrode active material were made different for each example as shown in Table 7 below. In Examples 3-2, 3-4, 3-6, 3-8, and 3-10, the negative electrode active material layer 162B has a multilayer structure. Furthermore, about Example 3 3-1 and 3-2, what mixed FEC and DEC by mass ratio 50:50 was used about electrolyte solution. In Examples 3-3 and 3-4, a mixture of FEC, DEC, and DFEC at a mass ratio of 30: 65: 5 was used as the electrolytic solution. In Examples 3-5 and 3-6, 1% by mass of sulfobenzoic anhydride (SBAH) was added to 100% by mass of FEC, DEC, and DFEC mixed at a mass ratio of 30: 65: 5 (100% by mass) as the electrolyte. We used what we did. In Examples 3-7 and 3-8, 1% by mass of anhydrous sulfopropionic acid (SPAH) was added to a mixture (100% by mass) of FEC, DEC, and DFEC as an electrolyte solution in a mass ratio of 30: 65: 5 (100% by mass). We used what we did. In Examples 3-9 and 3-10, a mixture of FEC, DEC, and DFEC at a mass ratio of 30: 65: 5 was used as the electrolyte, and 0.9 mol / dm 3 of LiPF 6 was used as the electrolyte salt. A mixture of 0.1 mol / dm 3 of LiBF 4 was used.

  Regarding the secondary batteries of Examples 3-1 to 3-10, the cycle characteristics were examined, and the bonding state of carbon contained in the negative electrode active material (the existence ratio as Si—C bonds) was also examined. Furthermore, each secondary battery after the charge / discharge cycle test was disassembled, and the amount of carbon and the amount of oxygen contained in each negative electrode active material layer 162B were measured. These results are shown in Table 7.

As shown in Table 7, a higher capacity retention ratio was obtained in Examples using FEC or DFEC as a solvent. Furthermore, it has been found that by including acid anhydrides such as anhydrous sulfobenzoic acid (SBAH) and anhydrous sulfopropionic acid (SPAH), even higher cycle characteristics can be obtained. Further, the cycle characteristics were improved by using LiBF 4 in addition to LiPF 6 as the electrolyte salt. That is, it has been clarified that a high effect can be obtained by including boron and fluorine in the electrolyte. For each electrolyte, even higher cycle characteristics were obtained by forming the negative electrode active material layer 162B in a multilayer structure.

  Although the present invention has been described with reference to the embodiments and examples, the present invention is not limited to the above embodiments and examples, and various modifications can be made. For example, in the above embodiments and examples, a cylindrical type, a laminate film type, and a square type secondary battery each having a wound type battery element (electrode body) have been described as specific examples. The present invention can be similarly applied to a secondary battery in which the exterior member has another shape such as a button type or a coin type, or a secondary battery having a battery element (electrode body) having another structure such as a laminated structure. Further, the present invention is not limited to the secondary battery, and can be similarly applied to the primary battery.

  Further, in the above embodiments and examples, the case where lithium is used as the electrode reactant has been described, but other group 1 elements in the long-period periodic table such as sodium (Na) or potassium (K), or magnesium Alternatively, the present invention can be applied to the case where a Group 2 element in a long-period periodic table such as calcium (Ca), another light metal such as aluminum, lithium, or an alloy thereof is used, and the same effect Can be obtained. At that time, a negative electrode active material, a positive electrode active material, a solvent, or the like that can occlude and release the electrode reactant is selected according to the electrode reactant.

It is the schematic showing the structure of the vapor deposition apparatus used for manufacture of the negative electrode of one embodiment in this invention. It is sectional drawing showing the structure of the negative electrode which concerns on one embodiment of this invention. It is sectional drawing showing the structure of the 1st battery using the negative electrode which concerns on one embodiment of this invention. It is sectional drawing which expands and represents a part of winding electrode body shown in FIG. It is a disassembled perspective view showing the structure of the 2nd battery using the negative electrode which concerns on one embodiment of this invention. It is sectional drawing showing the structure along the VII-VII cutting line of the winding electrode body shown in FIG. It is sectional drawing which expands and represents a part of winding electrode body shown in FIG. It is sectional drawing showing the structure of the 3rd battery using the negative electrode which concerns on one embodiment of this invention. It is sectional drawing showing the structure along the XX cutting line of the winding electrode body shown in FIG.

Explanation of symbols

  2 ... Deposition processing chamber, 2A, 2B ... Evaporation source installation area, 2C ... Deposition target traveling area, 3A, 3B ... Evaporation source, 31A, 31B ... Crucible, 32A, 32B ... Deposition substance, 4A, 4B ... Can roll, 6A, 6B ... shutter, 7, 8 ... take-up roller, 9-13 ... guide roller, 14 ... feed roller, 15 ... vacuum exhaust device, 16 ... partition plate, 17 ... partition wall, 101, 122A, 134A, 162A ... negative electrode Current collector, 102, 122B, 134B, 162B ... negative electrode active material layer, 111 ... battery can, 112, 113 ... insulating plate, 114 ... battery lid, 115 ... safety valve mechanism, 115A ... disk plate, 116 ... heat sensitive resistance element 117 ... gasket, 120, 130, 160 ... wound electrode body, 121, 133, 161 ... positive electrode, 121A, 133A, 161A ... positive electrode current collector, 121B, 33B, 161B ... positive electrode active material layer, 122, 134, 162 ... negative electrode, 123, 135, 163 ... separator, 124 ... center pin, 125, 131, 164 ... positive electrode lead, 126, 132, 165 ... negative electrode lead, 136 ... Electrolyte, 137 ... protective tape, 140 ... exterior member, 141 ... adhesion film, 151 ... exterior can, 152 ... insulating plate, 153 ... battery cover, 154 ... terminal plate, 155 ... positive electrode pin, 156 ... insulating case, 157 ... gasket 158 ... cleavage valve, 159 ... electrolyte injection hole, 159A ... sealing member.

Claims (8)

  1. The anode current collector, one or two of the compounds and oxygen anode active material or a compound of silicon containing carbon and oxygen and compounds of silicon are mixed comprising (O) a silicon containing-carbon (C) (Si) A negative electrode active material layer including a negative electrode active material having at least part of a phase of at least a seed is provided,
    The negative active material, Ri less than 25.0 atomic% der content of 11.0 atomic% or more oxygen along with the content of carbon is less than 3.9 atomic% 0.4 atom% or more,
    A negative electrode for a secondary battery, wherein 0.37% or more and 3.64% or less of silicon contained in the negative electrode active material exists as a Si—C bond.
  2. The negative electrode for a secondary battery according to claim 1, wherein the negative electrode active material layer has a multilayer structure in which a plurality of first and second layers having different oxygen contents are alternately stacked.
  3. The negative electrode for a secondary battery according to claim 1, wherein the negative electrode active material layer is formed by an electron beam heating vapor deposition method.
  4. A secondary battery comprising an electrolyte together with a positive electrode and a negative electrode,
    The negative electrode, the negative electrode current collector, the compounds and oxygen anode active material or a compound of silicon containing carbon and oxygen and compounds of silicon are mixed comprising (O) a silicon containing-carbon (C) (Si) A negative electrode active material layer including a negative electrode active material having at least a part of one or more phases is provided;
    The negative active material, Ri less than 25.0 atomic% der content of 11.0 atomic% or more oxygen along with the content of carbon is less than 3.9 atomic% 0.4 atom% or more,
    A secondary battery in which 0.37% or more and 3.64% or less of silicon contained in the negative electrode active material exists as Si—C bonds.
  5. The secondary battery according to claim 4, wherein the electrolyte includes, as a solvent, a fluorine-containing compound in which at least a part of hydrogen atoms in the cyclic carbonate or the chain carbonate is substituted with a fluorine atom.
  6. The secondary battery according to claim 5, wherein the cyclic carbonate is 4,5-difluoro-1,3-dioxolan-2-one.
  7. The secondary battery according to claim 4, wherein the electrolyte includes a solvent containing an acid anhydride.
  8. The secondary battery according to claim 4, wherein the electrolyte includes a lithium compound containing boron (B) and fluorine (F).
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